Composition comprising bis(2,3-epoxycyclopentyl) ether, a polycarboxylic acid anhydride and a polyol, and cured product thereof



provide appealing finishes.

melting component.

United States Patent 3,000,848 COMPOSITION COMPRISING -BIS(2,3-EPOXYCY- CLOPENTYL) ETHER, A POLYCARBOXYLIC ACID ANHYDRIDE AND A POLYOL, AND CURED PRODUCT THEREOF Charles W. McGary, Jr., and Charles '1. Patrick, Ir., South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Dec. 20, 1956, Ser. No. 629,475 9 Claims. (Cl. 26042) This invention relates to curable epoxide compositions and resins made therefrom. More particularly, this invention relates to curable compositions comprising bis- '(2,3-epoxycyclopentyl) ether, polycarboxylic acid anhydrides and polyols and resins made therefromi Our curable compositions are low viscosity liquids at temperatures ranging upwards from room temperature. These compositions are compatible with a wide variety of fillers and pigments which may be employed therein, if desired, to adjust the composition viscosity and at the same time enhance the physical properties of resins formedtherefrom. These compositions can be easily handled in such resin-forming applications as coating, bonding, laminating, molding, casting, potting and the like, without the need of solvents .or diluents although such solvents or diluentscan be used, if desired. In casting applications, our compositions can be made to fill smallintricacies of molds without applying high pressures or heating to high temperatures. In coating applications, they can be easily spread, brushed, orsprayed on surfaces by the many techniques available to the paint, lacquer and varnish industries. tions undergo negligible shrinkage when cured and are particularly useful in bonding, casting, molding and potting wherein undue shrinkage is particularly undesirable. Our compositions can be easily prepared using low temperatures at which no gelation occurs during preparation. However, they can be cured rapidly at higher temperatures. The pot-lives of our compositions can be controlled, as desired. These compositions can be made with relatively short pot-lives, of the order of a few minutes, with relatively long pot-lives, of the order of several hours or ofseveral days, or with pot-lives of intermediate duration, as desired.

Our resins are transparent and water-resistant. They can be made as hard, rigid infusible products, as tough, flexible, infusible products or as products having intermediate degrees of hardness and rigidity or toughness and flexibility, as desired. These resins can be machined to desired shapes and configurations and can be polished to They can be made as infusible products which are resistant to most organic solvents. Our resins can also be made as products having high heat distortion values, and are capable of sustaining heavy loads at high temperatures. In accordance with our invention, resins having combinations of any one or several of these useful properties can be produced.

Our curable compositions can be made by mixing bis- (2,3-epoxycyclopentyl) ether with a polycarboxylic acid anhydride and a polyol. Bis (2,3-epoxycyclopentyl) ether is a liquid having a viscosity of about 28 centipoises at about 27 C. In making homogeneous compositions it is advantageous to raise the temperature of the ether, anhydride and polyol'to the melting point of the highest Homogeneous compositions with liquid polyols and solid polycarboxylic acid anhydrides can be advantageously obtained by heating the anhydride to at least its melting point and adding it to bis(2,3- epoxycyclopentyl) ether and polyol, by heating a mixture of the ether, the polyol and anhydride to at least the melting point of the anhydride or by any other sequence These curable "composi- 3,h,848 Patented Sept. 19, 1961 which also involves the transformation of the anhydride to liquid form. Similarly, homogeneous compositions can be advantageously obtained with solid polyols by first heating them to at least their melting points. Stirring aids the formation of a homogeneous composition.

Acidic and basic catalysts can be added, if desired, to speed the rate of cure. Catalysts in amounts ranging up to 5.0 weight percent based on the weight of bis(2,3- epoxycyclopentyl) ether can be added at this point, at any time prior to curing or not at all, as desired. Higher catalystconcentrations above this range are also etfective, although concentrations of 5.0 weight percent and below have been found to be adequate. Catalyst concentrations of 0.001 to 5.0 weight percent based on the weight of bis(2,3-epoxycyclopentyl) ether are particularly preferred. This composition then can be cooled to room temperature and stored for future use, if desired, or used immediately. Other polyfunctional materials also may be incorporated into our curable compositions. Such polyfunctional materials include other polycpoxides, e.g., polyglycidyl ethers of polyhydric phenols and the like, low molecular weight urea-formaldehyde or phenol-formaldehyde polymers and the like. Many variations in the physical properties of our resins can be obtained by employing such other polyfunctional materials in our curable compositions.

Curing can be carried out by maintaining the curable compositions at temperatures from 50 C. to 250 C. Temperatures higher than 250 C. can be used, although some discoloration which may not be desired in the resin may result. The time for effecting a complete cure can be varied from several minutes to several hours.

It has been found that our compositions which contain difunctional polycarboxylic acid anhydrides, i.e., anhydrides having two carboxy equivalents, and difunctional polyols, i.e., polyols having two hydroxyl equivalents tend to form more flexible resins when cured than compositions containing anhydrides and polyols of greater functionality. Illustratively, a tough resin having a Barcol hardness of 48 was obtained in Example 15, hereinafter set forth, from a composition containing a difunctional anhydride and a difunctional polyol whereas a more rigid resin having a Barcol hardness of 53 was obtained in Example 34, hereinafter presented, from a composition containing a difunctional anhydride and a trifunctional polyol. It has been found, also, that our compositions which contain polycarbo-xylic acid anhydrides having greater numbers of atoms in the shortest carbon chain between the carbonyl groups of the oxydicarbonyl p,

or polyols having greater numbers of atoms in the shortest chain between hydroxyl groups tend to form more flexible resins when cured than compositions containing anhydrides or polyols which have fewer atoms in said shortest chains, respectively. Illustratively, arigid resin having a Barcol hardness of 17 was obtained in Example 1, below, from a composition containing maleic anhydride and ethylene glycol whereas a tough, flexible resin was obtained in Example 30, set forth below, from a composition containing maleic anhydride and a polyethylene glycol having an average molecular weight of about 400. Also a very rigid resin having a Barcol hardness of 53 was obtained in Example 34 from a composition containing maleic anhydride and glycerol whereas a flexible resin having a Barcol hardness of 0 was obtained in Example 35, hereinafter presented, from polyadipic and glycerol. Resins which have different degrees of flexibility or rigidity can be made in accordance with this invention to'fit particular requirements, as desired, by

' droxyl equivalents positions which contain equivalent of bis (2,3-epoxycyclopentyl) alkanol and a carbon atom group vpolyethylenepolypropylene glycols,

ybis(4 hydroxyphenyl) -2,2'-pr0pane,

,densation productsf, and the like, tree er acetylenic unsaturation and composed of carbon,

the selection of anhydrides and polyols for use in our curable compositions from which said resins are made. Our resins can be' made as infusible products which are water-resistant and insoluble in many organic solvents. As-an illustration, such infusible resins can be made from compositions which contain bis(2,3-epoxycyclopentyl) ether, polycarboxylic acid anhydrides in such amounts as provide about 0.33 to 4.00 carboxy equivalents of the anhydride for each epoxy equivalent of the ether and polyols in such amounts asprovide up to about 3.00 hyof the polyol for eachepoxy equivalent of the ether. Harder, infusible resins having high heat distortion values and which are also water-resistant and insoluble'in most organic solvents also can be obtained from our curable compositions. For example, harder resins of this type can be made from our curable combis(2,3-epoxycyclopentyl) ether, polycarboxylic acid anhydrides in such amounts as to provide 0.67 to.3.00 carboxy equivalents of the anhydride for .each epoxy equivalent of'b'is(2,3-epoxycyclopentyl). ether andpolyols in such amounts, as to provide from 0.16 to 1.67 hydroxyl equivalents for each epoxy ether.

By the term polyol, as used herein, is meant an organic compound having at least two hydroxyl groups whichare alcoholic hydroxyl groups, phenolic hydroxyl groups or both alcoholic and phenolic hydroxyl groups. Typical polyols can be represented by the general for- R islan alkyl group or hydrogen and can be the same or different for all Rs in the molecule. X can be a single bond or a divalent group composed of a carbon atom or group of carbon atoms interconnected by single or multiple bonds and to which such groups as hydrogen, alkyl, hydroxyl, amino, cyclic groups and the like or combinations thereof can be attached. X can also represent such divalent groups as oxyalkylene or polyoxyalkylene groups. X, as a divalent group may also contain nitrogen to which other groups, for example, hydrogen, alkyl,

represent cyclic groups, such as phenylene, cyclohexylene and the like. The Rs and X together with the carbon atoms, i.e., the Us of the formula, can represent a cyclic group such as phenylene, cyclohexylene and the like. The

presence of other groups, with the exception of tautomeric enolic groups, not specifically listed herein and not participating in the curing reaction is by no means harmful'and, in fact, can be useful in developing special properties in our resins. Mixtures of polyols or only one polyol can be employed in our curable compositions.

Representative polyols which can be employed in our compositions are polyhydric alcohols, such as, ethylene glycol, diethylene glycol, polyethylene glycols, propylene glycol,'tripropylene glycol, polypropylene glycols, trimethylcne glycol, butanediols, pentanediols, 2 ethyl 1,3 hexanediol, '2.-

, methyl-2,4-pentanediol, 12,13-tetracosanediol, Z-butene- 1,4-diol, 2 mcthoxymethyl-Q,4-dimethyl-l,S -pentanediQl, diethanolamine, triethanolamine, glycerol, polyglycerols, pentaerythritol, sorbitol, polyvinyl alcohols, cyclohexane- ,diols, cyclopentanediols, inositol, trimethylolphenol, and

polyhydric phenols, such as, dihydroxytoluenes, resorcinol, bis(4-hydroxyphenyl) methane, the polyhydric phenolic-formaldehyde con- Polyols which are h d q nmd xy m e a -hy q il Om n q ether oxygen connecting two otherwise unconnected carthe like may be attached or it may represent which contains sulfur. It can also bon atoms and having not more than 24 carbon atoms are preferred.

Polycarboxylic acid anhydrides useful in producing our resins can be represented by the formula:

wherein Y represents two or more carbon atoms interco'nn'ected'by single or double bonds and to which such interconnecting thecarbon atom groups towhich such other groups as previously mentioned maybe attached.

Y may also represent such cyclic groups as .phenylene,

cyclohexylene, cyclohexenylene, have one or more oxydicarhonyl Polycarboxylic acid anhydrides,

and the like which may containing other groups not specifically mentioned herein,-and not taking part in i anhydride, heptylsuccimc anhydride, pentenylsuccinic.

anhydride, octenylsuccinic anhydride, nonenylsuccinic anhydride, alpha, beta-diethylsuccinic anhydnide, maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, itaconic anhydride, citraconic anhydride, hexahydrophthalic anhydride, hexachlorphthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrachlorphthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, hereinafter referred to as chlorendic anhydride, tetrabromophthalic anhydride, tetraiodophthalic anhydride, phthalic anhydride, 4-nitrophthalic anhydride, 1,2-napthalic anhydride,.

1,8-naphthalic anhydride, 2,3-naphthalicvanhydride, 1,2, 4,5-benzenetetracarboxylic dianhydr ide, polymeric -di carboxylicacid anhydrides, or mixed polymeric dicarboxylic acid anhydrides such as those prepared by the auto'condensation of dicarboxylic acids, for example, adipic acid, pimelic acid, sebacic acid, hexahydroisophthalic acid, terephthalic-acid,'isophthalic acid, and the like. Also, other dicarboxylic acid anhydrides, useful in our curable compositions include the Diels-Alder adducts of maleic acid andaliphatic compounds having conjugated double bonds. Preferred polycarboxylic-acid anhydrides v are those which are soluble in bi s(2,3-epoxycyclopentyl) ether at temperatures below about 2507 C. Bis(2,3-epoxycyclopentyl) etheris a liquid diepoxy dicyclic aliphatic ether having a viscosity of about-28 centipoises at 27 C. The preparation of this diepoxide involves what can be termed epoxidation, or the controlled oxidation of the double bonds of bis(2-cyclopentenyl) ether which, itself, can be made fromcyclopentadiene by the successive steps of hydrochlorination and More specifically, bis( 2 c'yclopenr verse s l s cti n t. W

pentadiene groups attached thereto.

with hydrogen chloride in a suitable 'solvent,

sulfonic acid and the like.

such as, benzene, or without a solvent, for a period of about one hour at a low temperature such as C. to 0., thereby forming 1-chloro-2-cyclopentene. Subsequently, l-chloro-Z-cyclopentene can be subjected to alkaline hydrolysis with an aqueous solution of sodium carbonate or sodium hydroxide at a temperature of the order of 40 C. to 60 C. to form bis(Z-cyclopentenyl) ether. A substantially pure bis(2-cyclopentenyl) ether then can be obtained by any suitable separation procedure, for example, fractional distillation.

Suitable epoxidizing agents for the epoxidation reaction include peracetic acid and acetaldehyde monoperacetate. The epoxidation reaction can be advantageously carried out by charging bis(Z-cyclopentenyl) ether to a reaction vessel and then gradually adding the epoxidiziing agent. In order to provide ease of handling and to avoid the formation of highly concentrated or crystalline: peracetic acid with its attendant explosion hazard, the epoxidizing agent preferably is employed in a solvent, as for example, acetone, chloroform, methylethyl ketone, ethyl acetate, butyl acetate, and the like. Thereaction can be carried out at a temperature within the range of about C. to 150 0., although lower and higher'temperatures may be used. However, longer reaction times are needed at the lower temperatures to produce high yields. At the higher temperatures, side reactions from undesirable materials which can be removed, however, by conventional purification procedures, such as, fractional distillation. The reaction is continued until an analysis for epoxidizing agent indicates that an amount at. least sufficient to epoxidize all the double bonds of the bis(2- cyclopentenyl) ether has been consumed. In this connection it is desirable to employ an excess over the theoretical amount of peracetic acid to assure complete epoxidation. Upon discontinuance of the reaction, sidereaction products, solvent and unreacted material are removed by any convenient procedure, such as, by adding a potboiler, e.g., ethylbenzene, and stripping low-boiling materials. A liquid material, identified as bis(2,3-epoxycyclopentyl) ether, is obtained. Bis(2,3-epoxycyclopentyl) ether can be accepted as a residue product and subsequently further refined by distillation, extraction or crystallization, if desired. This product partially solidifies on standing at room temperature for 1 to 3 days .Which indicates the possible formation of a solid position isomer. This semi-solid bis(2,3-epoxycyclopentyl) ether can be liquefied by melting at a temperature of C. to C. and will remain a liquid for a period of several days at room temperatures.

Catalysts which can be employed, with advantageous effects in accelerating the cure of our compositions are the basic and acidic catalysts including strong alkalis, mineral acids and metal halide Lewis acids. Typical strong alkalis include the alkali metal hydroxides, e.g., sodium hydroxide and potassium hydroxide, and quaternary ammonium compounds, e.g., benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide and the like. Representative of mineral acids which can be used in speeding the formation of our resins are sulfuric acid, perchloric acid, polyphosphoric acid and the various sulfonic acids, such as, toluene sulfonic acid, benzene Metal halide Lewis acids which are also effective in speeding the cure of our resins include boron trifluoride, stannic chloride, zinc chloride,

.aluminum chloride, ferric chloride and the like. -The metal halide Lewis acid catalysts can also be used in the form of such complexes as etherate complexes and amine complexes, for example, boron trifiuoride-piperidine, and boron trifluoride-monoethylamine complexes. In the form of a complex, the metal halide Lewis acid catalyst is believed to remain substantially inactive until released as by dissociation of the complex upon increasing the temperature. When released from the complex, the catalyst then exerts its catalytic eifect.

Uniform dispersion of catalyst in our compositions prior to curing has been found to be desirable in order to obtain homogeneous resins and to minimize localized curing aroundcatalyst particles. Agitation of the compositions containing catalyst is adequate when the catalyst is miscible with said compositions. When the two are immiscible, the catalyst can be added in a solvent. Typical solvents for the catalysts include organic ethers, e.g., diethyl ether, dipropyl ether, Z-methoxy-l-propanol, organic esters, e.g., methyl acetate, ethyl acetate, ethylpropionate, organic ketones, e.g., acetone, methyl-isobutylketone, cyclohexanone, organic alcohols, e.g., methanol, cyclohexanol, propylene glycol and the like. The mineral acids and strong alkalis can be employed as solutions in Water, whereas metal halideLewis acid catalysts tend to decompose in water and aqueous solutions of such Lewis acids are not preferred.

Our curable compositions can be used in coatings, castings, moldings, bondings, laminates and the like in the manufacture of articles having a multitude of uses. These compositions can be colored by pigments and very appealing appearances may be imparted to articles made therefrom. Fillers can also beincorporated in our compositions so as to impart special properties to articles manufactured therefrom. Such sundry articles'as buttons, combs, brush handles, structural parts for instrument cabinets and the like can be formed through theuse of our curable compositions and resins. Of particular importance, are uses of our hard, tough resins of high heat distortion values in industrial applications wherein load carrying capabilities at high temperatures are required. Uses of this kind include hot fluid carrying conduits, high temperature tools and dies, minor structural parts and high temperature electrical insulation for highspeed aircraft and the like. Our polymerizable compositions are particularly useful in the manufacture of large tools as, for example, used in the automobile industries wherein the fluid nature of our compositions simplifies the construction of such tools. These compositions are particularly useful in the potting of electrical components wherein it may be desired to incorporate in the potting composition a heat conductive metal, such as, copper or aluminum.

Other useful compositions, and resins therefrom, can be made from polycarboxylic acid anhydrides, polyols and polyepoxides not otherwise mentioned herein. Resins having outstanding strength properties can be made from compositions containing polycarboxylic acid anhydrides and polyols, such as those specified herein, and dicyclopentadiene dioxide. Resins having excellent high temperature strengths can be made from compositions containing polycarboxylic acid anhydrides and polyols, such as those specified herein, and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylates, e.g., 3,4-epoxy-6-meth ylcyclohexylmethyl 3,4-epoxy 6 methylcyclohexanecar- .boxylate. Still other resins having many valuable properties can be prepared from various different compositions of polycarboxylic acid anhydrides and polyols, such as those specified herein, and, respectively, aliphatic diol =bis(3,4-epoxycyclohexanecarboxylates), e.g., diethylene glycol bis(3,4-epoxy 6 methylcyclohexanecarboxylate), aliphatic triol tris(3,4-epoxycyclohexanecarboxylates), e.g., 1,1,l-trimethylolpropane tris 3,4-epoxycyclohexanecarboxylates), bis(3,4-epoxycyclohexylmethyl) hydrocarbon dicarboxyla-tes, e.g., bis(3,4-epoxy l-methylcyclohexylmethyl) terephthalate, and 3,4-epoxycyclohexylmethyl epoxyalkanoates, e.g., 3,4-epoxy-6-methylcyclohexylmethyl 9,10-epoxystearate. Additional compositions which are useful in making resins having valuable properties can be made from polycarboxylic acid anhydrides and polyols, such as those specified herein, and, respectively, epoxidized butadiene polymers and copolymers and epoxidized olefinically unsaturated polyesters, e.g., an epoxidized 4-cyclohexene-1,2-clicarboxylic acid-polyhydric alcohol polyester. 3 I a Still other useful compositions and resins therefrom can be made from polycarboxylic acid anhydrides and polyhours. After this period,

lentand hydroxy 'respondingly listed in Table I. To

"mixture, was added. ""Each ol s, .su'ch as thos e specified herein and such polyepoxides as, respectively, diglycidyl ether, butadiene dioxide, di

1 glycidyl polyeth'ers of polyhydric alcohols,diglycidyl di- The following examples are'presented. Room temperatures, wherever given, are temperatures in the range from "25C. to 30 C. B arcol hardness values were determined at room temperature with a Barcol Impressor GYZI 93 4-1. jHeat distortion values and Izod impact values 'were determined in accordance with A.S.T.M. methods fD-i648-45T and D-25647T, respectively.

.. EXAMPLE 1 A mixture was prepared from 2.76 grams of bis(2,3-

V epoxycyclopentyl) ether, 2.45 grams of maleic anhydride and 0.31 gram of ethylene glycol. The mixture oohtained amounts of bis(2,3-epoxycyclopentyl) ether, ma-

leic anhydride and ethylene glycol such as to provide 1.67 'carboxy equivalents of the anhydride and 0.33 hydroxy equivalent of the glycol'for each epoxy'equivalent of the ether. This mixture was warmed until it became homogeneous at'a temperature not higher than 40 C. to

50 C; At a temperature within the range of 40 C. to

50C. the mixture had a viscosity which was similar to .Water at room temperature. ftainedat about 120 C. for f time' 'a' gel was formed.

The mixture was main- 14 minutes during which The gel was brought to and held at a'temp'eratu're of about 160 C. for a period of 2 a paleyellow, tough, infusible resin having a, Barcol'hardness of 17 was obtained.

EXAMPLE 2 A mixture containing 19.1 grams of bis(2,3-epoxy- 'cyclopentyl) ether, 13.7 grams of maleic anhydride and '2.2Lgram's of ethylene glycol was prepared. The amounts of bis(2,3-epoxycyc1opentyl) ether, maleic anhydride "and ethylene glycol contained by the mixture were such as to provide 1.33 carboxy equivalents of the anhydride and 0.33 hydroxy equivalent of the glycol for each epoxy equivalent of the ether. The mixture was warmed until it became homogeneous, occurring at a temperature of 40 C. to 50 C. The'viscosity of the mixture at a temperature in the range of 30 C. to 45 Tthat of water at room-temperature.

raised to a temperaturev of 80 6.75 hours duringwhich time a gel was formed. The temperature of the gel was C. Was similar to The mixture was C. and held there for raised to 160 C. and maintained thereat for 6 hours. After this time the temperature' was reduced to room temperature and a light amber, infusible resin having a Barcolhardness of 43 and an :Izo'd impact of 0.3 at room temperature and a heat distortion 'temperatureof 97 C. was

obtained.

EXAMPLES 3 THROUGH 7 Five'mixtures, each containing proportions of bis(2,3-

'epoxycyclopentyl) ether, maleic anhyd'rideand ethylene glycol," as correspondingly listed in Table I below were prepared. The amounts of bis(2,3-epoxycyclopentyl) ether, maleic anhydride and ethylene glycol contained by the respectiveequivalent per epoxy equivalent as coreach mixture 1 drop of a benzyl dir'nethylamine catalyst, said'drop containing g05 weight percent of catalystbased upon the weight of mixtureiwas heated until: "it i mixtures provided the carboxy equiva-' I for '6 hours.

became liomogeneous which occurred ata temperature of 40 C. to 50 C. The viscosity of the mixtures at temperatures within the above range were similar to the viscosity of water at room temperature. The mixtures were then heated to a temperature of C. and held there for 5 hours. The temperature was then raised to 120 C.

and maintained'thereat for 1.5 hours, afterwhich the I V C. and held thereat Gels formed from'every mixture in the times listed'in the table below. An infusible resin was obtained from each mixture having the physical proper ties correspondingly listed in Table I.

temperature was'again raised to 160 Table I Oar- Hy- Total gel time boxy V droxy Heat equivequiv- Bareol distor Example alent alent Gel Gel hard- ,tion Izod N 0. per per time, time, ness tem impact epoxy epoxy hours plus hours pera- 1 equivequiv- 80 at120 ture alent alent O.

EXAMPLES 8 THROUGHZQ I Twenty-four mixtures, each containing 0.91 grain of bis(2,3 epoxycyclopentyl) ether and the V amounts of maleic, anhydride and ethylene glycol as correspondingly listed in Table II below, were prepared. Each of the mixtures, thus prepared, contained amounts of bis(2.,3- epoxycyclopentyl) ether,maleic anhydride and ethylene glycol as to provide the carboxy equivalents of anhydride for each epoxy equivalent of bis(2,3-epoxy'cyclopenty1) ether and the aliphatic hydroxyl equivalents of the alcohol-for each epoxy equivalent of bis(2,3-epoxycyclopentyl) ether as listed in Table 11 below. Each mixture was heated untilitbecame' homogeneous, occurring at about 50 C. ,The homogeneous mixtures, thus formed,

'had the viscosities, at a temperature of 40 C., which were similar to the viscosity of Water at room temperature. The mixtures were then raised to a temperature of C. and held there until gels were formed. Gels formed from each mixture in thetimes correspondingly listed in Table III below. Each gel was maintained at 120 C. for'the timescorrespondin'gly listed in Table III. The gels were then raised to a temperature of, C. and held there for 6 hours. Infusible resins were obtained from each mixture These resins had properties which are correspondingly listed in Table III.

Table I1 V Garb oxy Aliphatic V We1ght of Weight of equivalents hydroxyl Example No. malelc ethylene per epoxy equivalents anhydride glycol equivalent per epoxy (grams) (grams) ratio equivalent 0. 16 0. 03 0.33 0.08 0.16 0.06 0.33 0. 17 0.16 0.12 0. 33 0.33 0.32 0.06 0. 67 0. 17 0. 32 0. 12 0.67 0. 33 0. 48 0.06 1. 00 0.17 0. 48 0.12 1. 00 0. 33 0. 64 0.12 1. 33 0. 33 O. 80 0.12 1. 67 0. 33 0.96 0. 12 2.00 O. 33 1. 12 0.12 r 2. 33 0.33 1.28 0.12 2.67 0. 1.44 0.12 3.00 0. 1.60 0. 12 3. 33 0. 1.76 0.12 3.67 0. V 0. 80 0. 36 1. 67 i 1. 0.80 0.48 1. 67 1. 0.80 0.60 1. 67 1. 1. 76 0. 36 3.67 1. 1.76 0.48 3. 67 1. 1.76 0.60 3. 67 1. .1.76 0.72 3. 67 2 9 Table III as correspondingly listed in Table IV below. Each mixture contained such amounts of bis(2,3-epoxycyclopentyl) Ex- Gel time Cure at ether, polycarboxylic acid anhydrides and polyhydric alamgle afig g Resin descriptmn at temperature cohols as provided 1.33 carboxy equivalents of anhydride and 0.33 aliphatic hydroxyl equivalent of the polyhydric 5 Amber tough Bare o1 hardness ofo alcohol for each epoxy equivalent of the bis(2,3-epoxy- 105 Do. cyclopentyl) ether. The mixtures were warmed until -3 ii ijgi lgg g gg gf gggf gg 3 34 they became homogeneous, occurring at temperatures be- 2Io Yellow, tough Barcol hardness 0f34 tween 40 C. and 100 C. The viscosity of each mixg 'g gfiggg gg gg ggf figjggggf 10 ture, at these temperatures, was similar to the viscosity 2.0 Pale-amber: Barcolhardness of 48. of water at room temperature. Each mixture was raised 8 gg gi fiiifigfiifi fiiifi f to a temperature of 120 C. and held there until gels 3-8 EEZ? gggg} 8; were formed. Gels were formed from each mixture in 20 Amber: tough, Barcol hardness of 0. the times correspondingly listed in Table IV. The mix- 38 B3: tures were maintained at 120 C. for periods of time, -0 Yellow. Barcolhardness 0f36- including the gel times, correspondingly listed in Table Z l, tough Barcolhardness of IV under the heading of Total Cure at 120 C. The Z-g gg' gel of Example 34 was heated to and held at 160 C. 7.0 Do. for 4 hours. The other gels were each raised to a temperature of 160 C. and held there for 6 hours. Infusible resins were obtained from each mixture. These resins EXAMPLE v were cooled to room temperature and were found to have A mixture was prepared from 2.76 grams of bis(2,3- the properties correspondingly listed in Table IV.

Table IV Ex- Grams of Grams of Gel tim Total ample Polycarboxylic acid anhy- Polyhydric alcohol poly; at 120 0. cure at Resin properties No. anhydride dride slilglfilc (hours) 32 Phthallc anhydride 0 99 Polyethylene glycol (average mo- 0.33 1 67 65.0 Tough, Barcol hardness of 37.

V lecular weight of 200). 33. Methyltetrahydrophthalic' l 00 Piflystlggl elilglygcfoiogaverage mo- 0.66 11 00 15.0 Hard. 34.-.. M i i c r i h y dride 0.65 Glgierol .l 0.10 0.57 20 Tough, Barcol hardness of 53. 35.--. Polyadipic anhydride 0.84 do 0.15 4. 50 6.5 Tough, flexible. 30-- Suecinic anhydride 0 67 ..do 0.15 1 00 6.5 Do.

epoxycyclopentyl) ether, 2.45 grams of maleic anhydride EXAMPLES 37 THROUGH 42 and of polyethylene: glyfml having average Six mixtures, each containing 0.91 gram of bis(2,3- molecular welght of This mlxture Contamed. Such epoxycyclopentyl) ether, 0.74 gram of phthalic anhydride amolints of b18625 'epoxycyclopentyl) h maleic and 0.33 gram of polyethylene glycol having an averhydnde 5 polyethylene glycol. as Pmvlded age molecular weight of about 200, were prepared. Each equlvalents of the anhydnde and 0'33.hydmXy1 mixture contained such amount of bis(2,3-epoxycycloeqmvalents of glycol each epoxy eqmvalent of 45 pentyl) ether, phthalic anhydride and polyethylene glycol The mlxmfe was to a temperature as to provide one carboxy equivalent of anhydride and tween 40 and a surfed to form,a homo 0.33 aliphatic hydroxyl equivalent of the polyethylene geneous mixture. oThlS mixture was then raised to a glycol for each epoxy equivalent of the biS(23 epoXy temperature of 120 and held thereat hours cyclopentyl) ether. Various acidic and basic catalysts A gel Was formed after. 2.5 hours at this temperature. 50 were added to each mixture The mixtures were then The gel was then maintained at 160 for an additional warmed to a temperature about whereupon 6 hours. A pale-yellow, tough, flexible, infusible resin they became homogeneous They were then heated to was formed' a temperature of C. and were held there until gels EXAMPLE 31 F were formed. Gels were formed from each mixture in A mixture was prepared from.0.91 gram of bis(2,3- thetirnes correspondingly listed in Table V below. epoxycyclopentyl) ether, 2.47 grams of chlorendic an- Table V hydride and 017 gram of polyethylene glycol having an average molecular weight of about 400. This mixture W ht G1 contained such amounts of bis(2,3-epoxycyclopentyl) Weight 3;? i, ether, chlorendic anhydride and polyethylene glycol as 60 fip at lyst ofcat acentt of atO120 "provided 1.33 carboxy equivalents of the anhydride and (grains) iff 0.085 hydroxyl equivalent of the glycol for each epoxy utes) equivalent of the ether. The mixture temperature was 1 raised to 50 C. to 60 C. and a homogeneous mixture 37 fijjg figfi'figfi gfgg iigge .00 0.44 was obtained. The temperature of this mixture was 65 38 Dimethylbenzylamine (as a 25 0. 005 0. 55 10s raised to 120 C. and held thereat for 6.45 hours. A m g g solutwn 1n e hyl gel was formed within 45 minutes at 120 C. The gel 39 Sulfuricaeid (as a25 weight percent 0. 005 0. 55 20 was cured for 6 additional hours at C. A tough, (asa25 Weight [LOO-5 O 55 infusible resin having a Barcol hardness of 35 was obpercent solutionin ethyl acetate). tamed. 70 l1 3I ())1g)entritluorlde-pngierldine complex. 0 039 4. 2 19;

' EXAMPLES 32 THROUGH 36 Five mixtures were prepared. Each mixture contained EXAMPLES 43 THROUGH 46 v0.91. gram ofbis(2,3-epoxycyclopentyl) ether and the Four mixtures, each containing 0.91 gram of bis(2,3- .amountsofvarious anhydrides and polyhydric alcohols 75 epoxycyclopentyl) ether, an amount of polycarboxylic raised to 160 tough, infusible resin having a gram of 1,2,

. the ether.

ace -s48 'acid anhydride as correspondingly/listed in Table'VI below and an amount 1; or polyhydric phenol also as correspondingly listed inTable'VI, were prepared. iEach'mixtu're contained s'uch amounts f of bis (2 ,3 epoxycyclopentyl) ether, poly'carboxylic acid a'nhydri'de and polyhymic phenol as provided the l number-"of, carboxy'equivalents of the-anhydride and the numb'er of 'hydroxyl equivalents of the phenoljfor eachv ep'oxy 'equiva'lent of-the ether' correspondin'gly listed i'n Table VI. l Each mixturewas warmed until it became homogeneous iand' then'heate'd to 120 C. They were'heldat-1'20 C.'for5;3 hours andthen were maintained at 160 1C.torfanadditional- 6 hours. 7 Light amber,'infus'ible resins having theproperties correspondingly listedin TableVI were obtained.

Table VI 1'2 temperature of 40 C. to "50 C. and became homogene- The temperature of themixture was raised to and held at 120 C. for Shours, during the fiI'StG /Z hours thereof a gel was formed. The temperature was increased to 160 C. and held thereat for 6 hours. Apale yellow, tough, flexible, infusible resin was obtained. q

EXAMPLE so A mixture was prepared from 2.73 grams of bis'(2',3- epoxycyclopentyl) ether, 1.38 grams of maleic anhydride and 0.32 gram of ethylene glycol. This mixture icontained such amounts of bis(2,3 epoxycyclopentyl) ether, maleic anhydride and ethylene glycol as toprovide '1.'00 carboxy equivalent of the anhydrideand 0.33 hydroxyl p t J I Carboxy Hydroxyi Exarn- Grams equivaequiva- Gel time ple Polycarboxylie of jPolyhydrio' phenol Grams of lents per lent per at 120C. Properties of resin 7 No. anhydride anhyr phenol epoxy epoxy (hours) dride equivaequivalent lent 43. :Meleic anhydride... 0.49 Polyhydrie condensation prod- 0.19 1. 0. 5. 33 Tough,.Bareol hardness of 42.

not of p-tertiary-butylphenol and formaldehyde (average V molecularweight of about 798). V

44- Phthalic anhydride. 0.37 Trimethylolphenol-.. 0.23 0.50 0. 50 1. 67 Tough, Barcol hardness of 38.

45. Suceinie anhydride 0. 38 Resoreinol 0. 13 0. 75 0. 3. 65 Tough, Barcol hardness of 41. A

46. Ohllrorgndic anhy- 0.93 Bisphenol A 0. 34 0. 50 0.30 0. 50 Tough, Barcol hardness of 34.

EXAMPLE 47 equivalent of'the glycol for each epoxy equivalent of the A mixture was prepared from 0.91 gram of bis(2,3- epoxycyclopentyl) ether, 0.3 gramof .phthalic anhydride and 0.31 gram of 1,2,6-hexanetriol. This mixture contained such amounts of bis(2,3-epoxycyclopentyl) ether,

and 1,2,6-hexanetriol as to provide phthalic anhydride 0.4 carboxy'equivalent of theanhydride and 0.7'hydroxyl equivalent of the-triol for-each;epoxy equivalent of the ether. To the mixture 0.02 gram of piperidine-borontri- 'fluoride complex catalyst (representing LO-Weight percent based on' the weight of'mixture) was added. Themixture 'was'heated to a temperature not higher than 100 C. and

became-homogeneous. The temperature of the mixture was then raised to 120 C. and maintained thereat for 2 /2 hours. A gel formed within the first 12 minutes of heating at 120 C. .Then the temperature of the mixture was C. and held thereatfor 6' hours. A brown, Barcol hardness of 35'was obtained.

EXAMPLE 48 A mixture containing 0.91 gram of bis(2,3-epoxycyclopentyl) ether, 0.3g'ram of phthalic anhydride and 0.31 6-hexanetriol was prepared. .This mixture contained such amounts of bis(2,3-epoxycyclopentyl) ether, phthalic anhydride and 1,2,6-hexanetriol as to provide 0.4 carboxy equivalent'of the anhydride and 0.7

hydroxyl'equivalent of the-triolfor each epoxy group of The mixture was heated to a temperature of less than 100 C. and became homogeneous. The temperature of the mixture was then raised to 120 C. and maintained thereat for 8 hours, during the first 6 /2 hours of which a gel was formed. The temperature was then raised to 160 C. and then held thereat for 6 hours. A pale amber, tough, infusible resin having a Barcol hardness of 22 wasobtained.

EXAMPLE 49 A mixture was prepared from 0.9l gram of bis(2,3-

4 epoxycyclopentyl) other, 0.1 gram of maleic anhydride and 0.6 gram of allyl 2,4,6-trimethylolphenyl ether. This mixwture contained such amounts of bis(2,3-epoxycyclopentyl) came homogeneous at this temperature. temperature was raised to C. and held thereat for a so as toprovide from from 0.16 .to 1.67 hydroxyl per :epoxy equivalent of said bis(2,3-epoxycyclopentyl) heated to about 45 C. and be- The-mixture ether. The mixture was period of 9 hours, during the first 65 minutes of which a gel was formed. The gel then was raised to a'temperature of C. and maintained thereat for-4 hours. A

yellow, tough, infusible resin having a Barcol hardness of 46 was obtained. 1

What is claimed is:

a polycarboxylic acid anhydride, and a polyol selected from the group consisting ofpolyhydric alcohols .and polyhydric phenols, in such relative amounts so as to provide from about 0.33 to 4.0 carboxy equivalents of said polycarboxylic acid anhydride and up to 3.0'hydroxyl equivalents of said .polyol per epoxy equivalent of. said bis(2,3-epoxycyclopentyl) ether.

2. 'An infusibile solid product obtained by reacting, at

elevated temperatures, the curable composition defined in claim 1.

3. A curable composition comprising bis( 2,-3 -epox'ycyclopentyl) ether, a polycarboxylic acid anhydride, and

a polyol selected from the group. consisting of polyhydric alcohols and polyhydric phenols, in such relative amounts 0.67Zto 3.0 carboxy equivalents of said polycarboxylic acid anhydride and from 0.16to 1.67

' hydroxyliequivalents of said polyol'per epoxy equivalent 7 of said bis(2,3-epoxycydopentyl) ether.

4. An infusible solid product obtained by reacting, at elevated temperatures; the curable composition defined in claim 3.

5. -Aninfusible solid product obtained; by reacting, at elevatedtemperatures, an admixture comprising bis(2,-3- epoxycyclopentyl) ether, maleic anhydride and glycerol, in suchrelative'amounts-so as'toprovide from-0.67 to 3.0 carboxy equivalents of said maleic anhydride and equivalents of said glycerol ether.

6. An infusible. solid product obtainedby reacting, at

elevated temperatures, an admixture comprising bis(2,3-

'epoxycyclopentyl) ether, succinic anhydride, and glycerol,

in such relative amounts =so as to-provide from0.67 -to 320 carboxy equivalents or said succinic' 1 from 0.16 to 1.67 hydroxyl equivalents of said glycerol per epoxy equivalent of said bis(2,3-epoxycyclopentyl) ether.

7. An infusible solid product obtained by reacting, at elevated temperatures, an admixture comprising bis(2,3- epoxycyclopentyl) ether, maleic anhydride and ethylene glycol, in such relative amounts so as to provide from 0.67 to 3.0 carboxy equivalents of said maleic anhydride and from 0.16 to 1.67 hydroxyl equivalents of said ethylene glycol per epoxy equivalent of said bis(2,3-

' epoxycyclopentyl) ether.

8. An infusible solid product obtained by reacting, at elevated temperatures, an admixture comprising bis(2,3- epoxycyclopentyl) ether, phthalic anhydride, and 1,2,6- hexanetriol, in such relative amounts so as to provide from 0.67 to 3.0 carboxy equivalents of said phthalic anhydride and from 0.16 to 1.67 hydroxyl equivalents of said 1,2,6-hexanetriol per epoxy equivalent of said bis(2,3- epoxycyclopentyl) ether.

9. An infusible solid product obtained by reacting, at elevated temperatures, an admixture comprising bis(2,3- epoxycyclopentyl) ether, succinic anhydride, and resorcinol, in such relative amounts so as to provide from 0.67 to 3.0 carboxyequivalents of said succinic anhydride and from 0.16 to 1.67 hydroxyl equivalents of said resorcinol per epoxy equivalent of said bis(2,3-epoxycyclopentyl) ether.

References Cited in the file of this patent UNITED STATES PATENTS 2,609,357 Koroly Sept. 2, 1952 2,720,500 Cody Oct. 11, 1955 2,739,161 Carlson Mar. 20, 1956 2,921,925 Phillips et al. Jan. 19, 1960 OTHER REFERENCES The Condensed Chemical Dictionary, 5th edition (1956), Reinhold Pub. Corp., New York. 

1. A CURABLE COMPOSITION COMPRISING BIS(2,3-EPOXYCYCLOPENTYL) ETHER, A POLYCARBOXYLIC ACID ANHYDRIDE, AND A POLYOL SELECTED FROM THE GROUP CONSISTING OF POLYHYDRIC ALCOHOLS AND POLYHYDRIC PHENOLS, IN SUCH RELATIVE AMOUNTS SO AS TO PROVIDE FROM ABOUT 0.33 TO 4.0 CARBOXY EQUIVALENTS OF SAID POLYCARBOXYLIC ACID ANHYDRIDE AND UP TO 3.0 HYDROXYL EQUIVALENTS OF SAID POLYOL PER EPOXY EQUIVALENT OF SAID BIS(2,3-EPOXYCYCLOPENTYL) ETHER. 